Starch conversion process



Aug. 31, 1943.

IS. M. CANTOR STARGH CONVERSION PROCESS Filed March 20.

Patented Aug. -3l, 1943 STARCH CONVERSION PROCESS Sidney Mark Cantor, Riverside, Ill., assignor to Corn Products Refining Company, New York, N. Y., a corporation of New Jersey Application March -20,1940, serial No. 325,036

5 Claims.

This invention relates to the conversion, by acid hydrolysis, of polymers of dextrose or other substances yielding dextrose, such as starch, cellulose, partially converted starch `"solutions (in the caseof two-stage conversions) and mother liquors (in reconversion procedures), for the production of syrup, such as starch syrup commercially known as glucose, high purity crystalline dextrose, pressed dextrose sugars, and block or slab dextrose sugars, forexample the socalled 70 and 80 corn sugars which contain all of the impurities of the converted liquors from which they are made.

In the production of these dextrose containing syrups and dextrose or dextrose containing sugarsfit has been customary for many years to neutralize the converted liquor with a sodium compound, usually-,sodium carbonate, in case the hydrolyzing acid is hydrochloric acid, which results in the formation in the liquor of the soluble salt, NaCl, which, because of its solubility, remalns in the liquor throughout the remaining steps of the process and is present in the final product in the case of 70 and 80 sugars, and in the hydrol 'or-nal mother liquor, in the case oi' high purity crystalline dextrose.

The presence of the salt is objectionable for several reasons: it contributes to undesirable coloration of the sugar-liquors and particularly of 70 and 80 sugars and hydrol; it tends to bring about an after crystallization in hydrol when the hydrol is shipped in tank cars or otherwise; it tends to inhibit the conversion of polysaccharides to dextrose in the conversion (referred to generally as reconversion) of `mother liquors; and, more particularly, it acts as a catalyzer tending to bring about or to promote and facilitate, in the reconversion operation which `consists in the depolymerization of higher molecular weight sugars back to dextrose, the polymerization-of dextrose to such higher molecular weight sugars; both reactions taking place or tending to take place simultaneously in the reconversion operation or in fact in any convertingoperation oi' this character.

This heretofore customary method of neutralization by a sodium compound is especially objectionable in the case of repeated conversions,

lf or example, when the conversion is interrupted,

the liquor neutralized and impurities removed and then the conversion continued, in order to increase the ilnal purity, as such procedure involves two neutralizations with resultant increase oi'salt content.

According to the present invention the acid is removed or eliminated from the liquor, in distinction to being neutralized, by treatment of the liquor with a substance, inert to dextrose, which will combine with the acid or acids in the liquor to form an insoluble salt or salts, in place of the soluble salt of the usual process, and

wherein N stands for nitrogen, X for two, one

or zero hydrogen atoms, and R for an alkyl, aryl, aralkyl or cyclic group, either substituted or unsubstituted, or any combination of these groups. Known examples of such compounds are theresinous condensation products 'of normal butyl amine, ethylenediamine, morpholine, triethanolamine, aniline and phenylmethylpyrazolone. the market and used for various industrial purposes. A

The essential thing is that the amine and the resultant amine salt shouldbe insoluble in water, so that the amine salt, which is an addition product of the amine and acid, may be removed from the converted liquor by filtration. Another essential islthat the amine be inert toward sugar type compounds, dextrose for example. Any amine characterized as above will serve the purpose of the present invention, or in fact any substance which is inert to dextrose insoluble in a dextrose solution and. which forms an insoluble addition product with acids may be employed.

An example'of a suitable amine for the purpose |is the r'eslnous condensation product of m-phenylene diamine and -formaldehyde which, with its method of production, is described in United States patent to W. H. Kirkpatrick, No. 2,106,486, patented January 25, 1938. This product may be considered as an amine, in the broad sense of the term intended herein, because its organic Iradical can be regarded as displacing hydrogen in ammonia. The term amine may be considered as including the aliphatic substance ormaldehyde as Well as the aromatic radical phenylene. n,

Another substance suitable for the purposes of The amine may These substances are available on 2 l l this invention is the substance known an Anex,

made by the International Filter Company, which substance is a resinous, water insoluble amine Vcondensation product, inert to dextrosey the present invention, the treatment also removes amino acids, in the form of insoluble salts, which under the old process were neutralized as soluble salts.

Experiments have demonstrated that the amount of protein and the amount of color in a converter liquor treated with the acid removing substance of the present invention are very considerably less than the protein and color in a liquor neutralized with an alkaline sodium compound. The following appears to be the explanation f or this:

Starch employed for conversion contains a small amount of protein. The protein is ordina'rily not completely separated from the starch by the starch tabling and washing operations.

This residual protein is one of the chief contributhe hydrolytic action of the converter acid, theI intended function of which acid is, of course, the

hydrclyzation or conversion of the starch to dextrose.

According to the present invention the hydrolyzed proteinin the form of amino acids is removed by the converting acid removing substance which will react with these amino acids in the same way as it reacts with the converting acid to form insoluble salts removable by filtration, Tests show that the amine is capable of removing about 60% of the protein present in the converter liquor. Preferably, the treatment for removal of the amino acids (as well as the other acid) follows as closely as possible the conacids. Applicants process is advantageous in the case -of processes involving a single conversion. `It has greater advantages, over the alkali neutralization procedure, where the converted liquor is subjected to reconversion since each conversion, when followed by alkali ncutralization, adds to the quantity of soluble salt 'in the liquor, in the final products, and in fact,

in lall stages of the process particularly where, 'as is now customary in the production of high purity, crystalline dextrose, melted, unwashed second or third sugars are mixed with the original converted liquor.

The effect of the `herein disclosed method of acid removal is particularly marked under these circumstances. For example, where first greens are to be reconverted and recrystallized, the color in the first greens, treated by the process of this invention, is so greatly reduced, in comparison with rst greens neutralized with sodium carbonate, that the second sugar produced from the recrystallized first greens is almost equal in quality, particularly as to color, to a iirst sugar, so that this second sugar, instead of being remelted and recrystallized, as has been customary, may be sold as a high quality sugar.

It is necessary at intervals to regenerate the amine or other acid removing substance. This can be done by treating it with an alkaline solution, suolias a 1/% to 2% caustic soda or car- ,bonate of soda solution, which disassociates the acid from the amine addition product in the form.

of a soluble salt which is then Washed out of the amine substance with water.

The invention is illustrated in the accompanyl ing flow sheetin which Fig. 1 illustrates the application of the invention to a two-convei'sion process in which the second sugar is a high purity sugar; and

Fig. 2 its application to a process in which the conversion of starch is interrupted; the converting acid, amino acids and other non-carbohydrate substances being removed by treatment in accordance with this invention, and the liquor reconverted to a purity higher than would be possible under-similar conditions by a single conversion.

The process illustrated in Fig. 2 may be regarded as an improvement upon the process of United States Patent No. 1,876,883, September 13, 1932, to VEbert et al. In the Ebert et al. process the neutralization of the converted liquor at two stages brings about an undesirable increase in salt content and color in the converted liquor l y out in the usual autoclave into which is intro# duced the dextrose polymer, starch for example,

verting operation for the reason that the reaction between the amino acids and the dextrose or dextrose dehydration products tends to occur as soon as and wherever these substances are in contact with each other.

is not altogether clear but is probably due to the changein the iso-electric point of the colloids brought about by partial removal of the amino water and acid. The converted liquor is passed through a granular mass-of the acid removing substance as indicated at II, and the liquor from this step is then filtered at I2, ordinarily without centrifuging in the usual mud centrifugals. The liquor is kept in contact with the granular bed at I I until the usual pH of 4.5 to 5.5 is reached, the insoluble salts remaining in the granular bed. The filtration at I2 is for the purpose of removing fatty acids and other'non-carbohydrate material. The iiltered liquor may then be refined and concentrated as indicated at I3. The refining involves ordinarily an adsorption treatment over bone black or by admixture of activated vegetable carbon followed by filtration; and the adsorption operation, as well as concentration,

may be carried out in two stages, each concentration being followed by adsorption treatment.

The conversion may be to the so-called glucose stage, if the end product is to ybea starch syrup, or it may be carried to a higher purity, and subsequently crystallized either for high purity crystallinev dextrose or for the production of 70 or 80 or other dextrose sugar. f

Assuming as an illustration thatl the process involves conversion of starch and the'production of high purity crystalline dextrose, the process will be substantially as follows: 11 Baume starch liquor (-13 Baume) is introduced intothe autoclave i0 withV enough hydrochloric acid to give the liquor a pH of 1.5 (1.4-1.8) and the starch converted for minutes (l5-30 minutes)v after about 45 pounds steam pressure has been reached, or until the purity (reducing sugar calculated as dextrose) is about 90. The converted liquor is then run through a column or tower il containing the acid removing substance in granular form until enough acid has been removed to give the liquor a pH of 5.0 (4.5-5.5); whereupon the liquor is filtered at I2, in any suitable type of illter or illter press. The filtered liquor is then concentrated in a lvacuum pan. to 26 Baum (-28 Baume), is passed through bone char filters, concentrated in a finishing pan I(to 39 Baume (37.5-41.51Baum) arid is again put through bone black, these operations being indicated at I3, and is ilnally introduced into the crystallizer i4 and crystallized in motion accord- Ving to the general principles of the processes described in United States patents toWilliam B. Newkirk, No. 1,471,347, granted'October 23, 1923, No. 1,508,569, granted September 16, 1924, and No. 1,521,830, granted January 6, 1925, on which the herein described process is an improvement. Themassecuite is centrifuged at I5 to remove mother liquor and the crystals washed in the centrifugal machine. One of the advantages of thel present invention is that the crystallizing period is considerably shortened.

The mother liquor may be reconcentrated (if desired'after reconversion) and then crystallized for a second yield of dextrose, which because of its high purity and good color, due to the present acid removal treatment, may be marketed as such; or it may be melted and mixed with fresh converter liquor at I0 as the process proceeds in accordance with usual current practice.

The reconversion step is indicated at I8 with the liquor acidiiled to a pH of 1.6 (1.6 to 1.9) and converted for 18 minutes (15 to 20 minutes), after a steam pressure of about pounds has been developed in the autoclave, or until the purity is about 90.v The reconverted liquor is then run through a column or tower I1 containing the acid remover until enough acid has been removed to give the liquor a pH of 5.0 (4.5 to 5.5) whereupon the liquor is iiltered at I8, refined and concentrated to 39" Baume (37.5 to 41.5 Baume) at I9, crystallized in motion at 20 and centrifuged and washed at 2 I.

The second sugar produced by this operation will, because of the method of acid removal in place of the usual neutralization, -be of such high t purity and brilliant color as to make it Asaleable as a high quality dextrose. Because improvements in the process of making crystalline dextrose have resulted in the removal oi larger quantities of dextrose from the converted liquor in the ilrst crystallizing operation leaving a poorer first greens for the second crystallization, which yields a more or less impure and colored second y is repeated at 21 from the amine.

melt the second sugar and return the melt to the ilrst crystallization, particularly where color v is increased by step.

One of the advantages of the present process is that a second sugar may be produced which in purity and color compares favorably with rst sugars.

The two-stage conversion process illustrated in employment of the reconversion Fig. 2 may be described as follows:

18 Baum starch liquor (LP-20 Baume) with suiilcient hydrochloric acid to give the converter liquor a pH oi' 1.5' (L4-1:8) is converted in the autoclave 22 at 45 pounds steam pressure for 8 minutes (5-10 minutes) or until a purity of 40 (3S-50) is obtained. The converted liquor is then passed through a bed oi' the acid remover, at 23, until suillcient acid has been removed to raise the pH to 5.0 (4.5-5.5), after which the liquor is ilitered at 24, diluted-With water at 25 to l2 Baulm (l0-13 Baume), and re-acidified with hydrochloric acid to a pH of 1.5 (1.4-1.8). The liquor is then converted as indicated at 26 at 45 pounds steam pressure for 9 minutes (8-10 minutes) or until a purity of 95191-) isobtained; whereupon the treatment with the acid remover (4.5-5.5), the liquor ltered at 28, refined and concentrated at 29 to a density of 39 Baume (3842 Baume) and crystallized inrmotion at 30, the crystallizing operation requiring only about 4 days (3l/2 to 4/2 days) instead of the usual 5 or 6 days. The massecuite is centrifuged at 3i, the crystals washed with water in the centrifugal machine and the wash water returned,

through conduit 32, to either the rst conversion at 22, or, preferably, to the second conversion at 26. -The mother liquor discharged from the centrifugal machines maybe treated, with or without reconversion, for a second yield of crystal sugar.

In any process according to the present invention, it will be necessary to regenerate the acid removing substance at intervals to disassociate therefrom the added acid. Referring to Figs. l or 2, this may be accomplished by stopping the process, and passing an alkali regenerating agent. for example, a dilute caustic soda solution, in-

troduced at 33 through the bed of the amine substance. The caustic soda combines with the acid 'added to the amine forming a soluble salt which is discharged at 34. Theoretically any alkaline compound may be used for disassociating the acid erable since they form soluble salts with the acid.

Instead oi' using hydrochloric acid for the con version, any other usual converting acid may be used suchl as sulfuric acid. While it has been more usual to employ hydrochloric acid for starch conversion than sulfuric acid, there is a substantial advantage in employing sulfuric acid when the acid removing process of the present invention is used, i'or the reason that the acid removing material will removela larger quantityof sulfuric acid, due to the fact that it is less vhighly ionized than hydrochloric acid and therefore comto give the liquor a pH of 5.0

Sodium CQmpOUIldS are pIEfnot be removed from the concentrated'liquor,

practically. by a illtering operation. Applicants process is, therefore, essentially difierent from the process of using sulfuric acid and neutralizing with a calcium compound, since inapplicant's process the salt is insoluble at all dextrose concentrations. This is what is meant herein by the term insoluble" as applied `to applicants combination of acidand acid removing substance.

The term "converted liquor," or equivalent phrase, as used herein, includes a partially converted liquor. as` in the production oi starch 'syrups, as well as a liquor in which the conversion to dextrose is carried as far as possible, as is usual in the production of high purity crystalline dextrose or lower purity dextrose sugars.

The two-stage conversion makes it possible to use the higher initial gravity indicated. This results in a higher purity liquor for conversion and a higher yield, without the usual disadvantage of increased salt content in the final hydroh (The examples of the application oi thevinvention to practice given above are to be considered as merely informative and typical. The intention is to cover all equivalent processes and all modifications of the disclosed processes within the scope of the appended claims.

It has been proposed to remove the salt, due' to alkali neutralization, from hydrols and other dextrose containing liquors by dialysis. Ap,- plicants invention obviously makes such procedure unnecessary.

Other advantages of the. improvement constituting the present invention may be summarized as follows: increased purity of the neutralized liquor and of the final product; reduced color in the product; increased yield in the case of high purity crystalline dextrose production; an 80% reduction of salt in the hydrol whereby the tendency of the hydrol to crystallize in storage or transit is decreased; employment throughout the process of higher purity liquors, especially in processes involving repeated conversions and crystallizations yielding, for example, a second sugar of almost as high purity as the first sugars shortening oi the crystallizing time, more particularly in processes involving two-stage conversions; increased production oi dextrose more pronounced when mother liquors are reconverted;

and elimination of one step of the refining process. viz., separation of mud by centrifuging.

I claim: l. In the art of producing dextrose, or dextrose containing products, by the acid conversion of dextrose polymers, the improvement which consists` in bringing the converted liquor into contact with anl amine, represented by the formula R-N-X wherein N stands for nitrogen, X for 0 to 2 atoms oi' hydrogem. and R for a member of the class consisting of alkyl, aryl, aralkyl and cyclic groups of the primary, secondary and tertiary types substituted and unsubstituted and combinations of these groups. which amine is inert to dextrose and of sumciently high molecular weight to be capable ofv forming an insoluble compound with acid in the converted liquor; and effecting a removal between said insoluble compound and said converted liquor, whereby acid is removed from said concerted liquor.

2. The', process of claim 1 in which the converted liquor is caused to pass through a granular bed of amine for the purpose of bringing about the reaction between said amine and the acid in the converted liquor.

3. The process of claim 1 in which the converted liquor, after removal of acid, is refined, concentrated and crystallized, and the dextrose removed therefrom in a crystalline state and at high purity.

,y 4. In the treatment of acid-containing dextrose polymer hydrolysate liquor, bringing the liquor into contact with a substance represented by the formula Rf-N-X, wherein N stands for nitrogen, X for 0 to 2 atoms of hydrogen, and R for a member of the class consisting of alkyl, aryl, aralkyl andicyclic groups substituted and uny hydrolysate liquor into contact -with an insoluble resinous reaction product of m-phenylene diamine and formaldehyde, which product is inert with respect to dextrose and capable of forming insoluble material by reaction with acid in such liquor whereby acid -is removed from the liquor.'

SIDNEY MARK CANI'OR.y 

